Process for the treatment of fibrous materials



Patented Apr. 19, 1938 UNITED ,STATES PATENT OFFICE PROCESS FOR THE TREATMENT OF FIBROUS MATERIALS Walter Kling andEi-nst Giitte, Chemnitz, Germany, assignors to Boehme Fettchemie-Gesellschaft m. b. 1-1., Chemnitz, Germany No Drawing. Application August 28, 1935, Se-

rial No. 38,325. In Germany August 28, 1934 6 Claims.

jected to the action of compounds which yield' surface active cations (hereafter called cation active compounds), for instance the high molecular quaternary ammonium compounds.

As is set forth in the prior application of -Kling, Giitte et al., filed September 18, 1934, Serial No. 744,606, it has already been discovered that decided improvement can be effected in dyeing processes of greatly varied character by the use of cation active substances, greater amnity for of the dye color being obtained, and various other advantages secured, all of which are outlined in full in the application hereinbefore referred to. It is now found, however, that while the use of cation active substances in connection with dyeing processes is highlydesirable, there are certain attendant difficulties which it is the object of the present invention to avoid. For instance, it is found that the cation active substances when used either preliminarily, subsequently, or with the dye bath, frequently affect alteration of the shade of the dye and greatly reduce the resistance to fading. The same is found to be true of fibrous material dyed in the normal way and subsequently toned or matted with cation active sub stances. It is also found that the usual methods of increasing the resistance to fading, for instance by subsequent chromium and copper treatment, are less effective where the material has been initially subjected to the action of cation active substances.

These various defects may be avoided if, after dyeing, matting, or toning with cation active substances, the material is subjected to a subsequent treatment with an acid radical compound yielding in watery solution anions of an equivalent weight'of at least 90 but preferably 150 or higher, and capable of reacting with the cation active substances to produce a water insoluble precipi- 45 tate, for instance Turkey red oil, resin soap or tannin. The necessary quantities are quite small; thus a rinsing bath containing 0,5 grams per liter of 25% sumac extract, is fully sufiicient. The term- "tannin is used herein to include the varactive substances may be employed in lieu of the a Turkey red oil, resin soap, or tannin, although these are less effective. For example we may the fibers being imparted to the dyes, a deepening ious derivatives and extracts, all of which are use persulphates, perborates, ortho-, meta-, and pyropho'sphoric acids, as well as the various soluble salts of these acids, further, soluble complex salts such as complex cyanides. The following compounds are specifically recommended for use in the manner herein explained, it being observed that the employment-of compounds which are not sensitive to iron salts, which are sometimes present in dye or treatment baths, is desirable:

Turkey red oiland other sulphonated oils and sulphonated fatty acids, resin soap made by dissolving colophony in sodium hydroxide solution, the sodium salt of abietic acid, the potassium salt of hydroabietic acid, tannin and synthetic tanning agents, f. e. Neradol, sodium pyrophosphate, primary, secondary, and tertiary} alkali metal ortho-phosphates, ammonium metaphosphate, alkali metal metaphosphates, potassium persulfate, ammonium persulfate, sodium perbor'ate, sodium perphosphate, potassium zinc cyanide, sodium ferrocyanide.

The temperature can be ordinary or moderately elevated temperature, more than 60 C. being less suitable. The pH value of the treatment liquid containing the acid radical compound of high molecular weight should suitably be between '7 and 4, higher acidities being deleterious for most textile materials.

In the case of the following dyes which have been applied to fibrous materials treated, as outlined in the previously filed application hereinbefore mentioned, with a cation active substance, very remarkableimprovements in the reproduction of the proper shade and in the resistance to fading is noted when these materials are subsequently treated with Turkey red oil, resin soap or tannin or other compounds mentioned herein.

I Schultz,.Farbstofitabellen (Dye Tcbles) 7th edition, vol. 1 Diamin brown M No. 412 Direct true yellow BFF -No. 935 Direct brown B, -No. 415 Pluto-orange G 'No. 480' Benzo-purple 4 B; No. 448 Brilliantbenzo-violet 2 RL No. 610

The following specific examples illustrate the ried into practice, it being understood that we do not necessarily confine ourselves to the details included herein.

Example 1 Cotton piece goods are dyed as usual with 3% Diamin brown M using for 1 kg. of'cotton 300 litres of a dyebath containing 10% by weight Glaubers salt at temperatures from 50-80 for -60 minutes. nated for 15-25 minutes with a solution of 1,2 grams per litre dodecyl pyridinium'sulphate and dried once more. The dried piece is then treated The piece is then dried, impreg- 4 with a solution of 0,5 grams per litre of sodium abietinate at ordinary temperature and at a pH value 01' 7. Finally the fabric is dried.

. Example 2 Knitted goods made of viscose rayon are dyed as usual with 2% Direct brown B using for 1 kg.

ordinary temperature and at a pH value of 4,

produced by acidulating the pyrophosphate solution by means of acetic acid. Finally the fabric is dried. I 7

Example 3 Cotton yarn is. dyed as usual with 2,5% Direct true yellow BFF using for- 1 kg. of yarn 300 litres of a 12% Glaubers salt solution at temperatures from 50-80 C. for 45 minutes. The yarn is then centrifuged and dried and treated during 20 minutes with a solution of 1,5 grams per litre of the quaternary ammonium salt derived from diethyl-aminoethyloleylamine by addition of dimethyl sulfate. The yarn is dried once more and impregnated during 20 minutes with a solution of 2 grams per litre of potassium persulfate at 40 C. and at a pH value of '7. Finally the yarn is dried.

1 Example 4 0 Cotton fabric is dyed as usual with 4% Pluto orange G using for 1 kg. of fabric 300 litres of a 15% Glaubers salt solution at temperatures near the boiling point for 45-60 minutes; The fabric is then driedand treated for 15 minutes at 30 C. with a solution of 2 grams of triethyl cetyl ammonium bromide, squeezed, dried and impregnated at ordinary temperature during 20 minutes with a solution of sodium metaphosphate. Finally the fabric is dried.

Example 5 Cuprammonium rayon is dyed as usual with 3% Benzo purple 43 using for 1 kg. of rayon 300 litres of a 10% .Glaubers salt solution, at temperatures from 50-80 C. for 30 minutes. The fabric is then dried, treated witha solution of 3 grams per. litre of the addition product of tetradecyl bromide to hexamethylenetetramine, squeezed out and dried. Then the fabric is impregnated with a solution of 1 gram per litre of resin soap (prepared by dissolving colophony in sodium hydroxide solution) at ordinary temperature during 20 minutes. The fabric is then squeezed and dried.

Example 6 o Viscose rayon yarn is dyed as described in Example 5 with 3% Brilliant benzo violet B. The dried fabric is impregnated with an addition product of the tetradecyl ether of war-glycerine. brdmhydrine C1aHzwCHaQCHaCHOI-LCHzBr to pyridin during 5' minutes, squeezed and dried. Then the fabric is treated with a solution of 2 grams per litre of potassium perphosphate during 15 minutes at 30C. and dried. Example 7 Q grams per litre of a matting agent made as follows:

About four hundred grams of zinc sulphide are mixed with one hundred cc. of a solution of cocoanut oil fatty alcohol sulphonates containing 30%, calculatedon free alcohol. After the re sulting emulsion is thoroughly mixed, 2. solution of grams of the quaternary ammonium salts derived from dodecyl sulphuric esters and a commercial mixture of pyridine bases is introduced. The mass is then stirred until the electro-neutral compound formed has precipitated. After the precipitate has been separated from the clear -solution, the former is peptized by adding a solution containing 64 grams of the above quaternary salt and 250 cc. of glycerine. The yarn is then rinsed with water of 60 C. and squeezed out. The fastness to light which was reduced by the matting treatment is restored to the dyed yarn by a treatment with a solution of 0,5 grams per litre of Turkey red oil (containing 37% fatty matter) at ordinary temperature for 15 minutes. Finally the yarn is dried.

Example 8 Viscose rayon yarn dyed and matted as described in Example 7 is treated with a solution of 0,25 g. of light tannin at 30 C. for 15 minutes and dried.

Among the more important compounds which yield surface active cations are the high molecular quaternary ammonium compounds, ammonium salts containing high molecular aliphatic residues, and in particular the compounds derived from heterocyclic nitrogen bases, such as the pyridine bases, these being the most readily acpounds derived from aliphatic tertiary amines,

for example triethyl cetyl ammonium iodide or bromide.

'In the preliminary treatment of the fibrous material, in lieu of the quaternary ammonium compounds, the analogous high molecular phosphonium or sulphonium compounds may be used,

for instance decyl phosphonium iodide, dodecyl phosphonium bromide, tetradecyl phosphonium bromide, octadecenyl phosphonium iodide, dodecyl sulphonium bromide.

The following compounds have proven satisfactory in addition to those mentioned specifically hereinbefore: Tetradecyl, hexadecyl, and cotadecyl pyridiniuni sulphate, undecenyl, dodecyl, tetradecyl, octadecyl, octadecenyl chinolinium sulphate, decyl pyridinium bromide, hexadecenyl chinolinium iodide, quaternary ammonium compounds derived from asymmetrical oleyl-diethylethylenediamine by addition of dimethyl sulphate or diethyl sulphate or methyl iodide, heptyliurea bromide, decylithiourea iodide, hexadecylithioureaiodide, the addition products of tetradecyl bromide or do'decyl iodide to hexaiodide, octadecyl sulphonium vmethylenetetramine, heptyl guanidine, tolyl guan- Addition product of tetradeoyl bromide to hexaidine, the quaternary ammonium compound prepared by the addition of the dodecyl ether of aglycerine bromhydrine CnHzaCH2.O.CHz.CHOH.

CHzBr to pyridin, and the quaternary ammo-.

CUB OSOJI Octadecenyl quinolinium iodide 051191 Heptyl isourea bromide [HzN.C(O.C-zI-I15) :NHlBr Decvl isothiourea iodide [H2N.C(S.C1oI-Iz1) :NHJI

methylenetetramine 014115 I [(CH|)N:]N\

Br 'Heptyl guanidine HzN I HQN - Addition product of 'glycerine bromhydrine dodecyl ether to pyridine Addition product of bromine-acetic acid dodecyl ester of quinoline omoooomonna These compounds may be added either directly to the dye bath or employed for preliminary .treatment of the material to be dyed. Thus, as pointed out in the prior application hereinbefore mentioned, an extraordinary deepening of the dye color may be obtained, if, for example, a vegetable fibrous material -is pretreated with a substance giving off surface active cations in aqueous solution and thereafter dyed with direct dyestufis. By means of such pretreatment it is not 'only possible to promote the absorption of direct dyes by vegetable fibers, but the process is even applicable to the satisfactory dyeing of wool and the like by such dyes which normally do not adhere to animal fibers.

When any of the foregoing compounds are used for the purpose of improving the dyeing of fibrous materials of any nature, the precipitation thereof as outlined herein with the various acids or salts mentioned above will be found to very decidedly improve the resistance of the dyed material to light and to, enhance the color of the dyed material.

Having thus described the invention, what is claimed as new and desired to be secured by Letters Patent'is: i

1. The process of treating fibrous materials which comprises subjecting the material to the action of a dye bath containing a substance yielding surface active cations, and thereafter applying to the material a soluble resin acid radical compound reacting with the cation active substance to produce a water insoluble precipitate.

2. The process of improving. the resistance to fading of dyed fibrous material which has been:

treated with a cation active substance which comprises treating the material with a soluble resin acid radical compound reacting with thecation active substance to produce a water insoluble precipitate.

3. The process of improving fibrous materials which comprises treating the material with a dye and with a substance yielding surface active cations, and thereafter applying to the material a soluble resin acid radical compound reacting with the cation active substance to produce a water insoluble precipitate.

4. The process of improving fibrous materials which comprises treating the material with a dye and with a high molecular quaternary annnonium compound, and thereafter subjecting the material to the action of a resin acid. 7

5. The process of treating natural or regenerated cellulose materials which comprises subjecting the material to the action of a direct dye bath containing a substance yielding surface active cations, and thereafter applying to the material a soluble resin acid radical compound reacting with the cation active substance to produce a water insoluble precipitate.

6. The process of treating natural or regenerated cellulose materials which comprises subjecting the material to the action of a direct dye bath containing a substance yielding surface active cations, and thereafter treating the material with a resin acid.

WALTER grime. ERNST Go'rm. 

